Process for the continuous dyeing of synthetic fiber materials with diphenoxy anthraquinone dyestuffs

ABSTRACT

The process for the continuous dyeing of synthetic fiber materials in which the fiber materials are impregnated with a dyeing liquor comprising an organic solvent and an anthraquinone dyestuff of formula   IN WHICH B and B&#39;&#39; independently of one another represent a C1C9- alkyl, cycloalkyl or aralkyl radical, Ha1 and Ha1&#39;&#39; denote a halogen atom, each of m and n is a number from 0-3, with the proviso that the sum of m+n is at least 1, and each of p and q is a number from 0-2; and the dyed materials are subsequently subjected to a heat treatment. The dyeings obtained are distinguished by high dyestuff yield, very good buildup and excellent fastness properties, especially very good fastness to thermofixing, washing, rubbing and light.

United States Patent Wegner et al.

[ 1 Feb. 15, 1972 [54] PROCESS FOR THE CONTINUOUS DYEING OF SYNTHETICFIBER MATERIALS WITH DIPI-IENOXY ANTHRAQUINONE DYESTUFFS [72] Inventors:Peter Wegner, Cologne; Rutger Neeif,

Leverkusen; Robert Kuth, Cologne, all of Germany [73] Assignee:Farbeniabriken Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: Aug. 3, 1970 [21] Appl. No.: 60,738

3,5l0,243 5/1970 Seuretetal ..8/39

Primary Examiner-George F. Lesmes Assistant ExaminerT. J. Herbert, Jr.

Attorney-Plumley & Tyner [5 7] ABSTRACT The process for the continuousdyeing of synthetic fiber materials in which the fiber materials areimpregnated with a dyeing liquor comprising an organic solvent and ananthraquinone dyestutf of formula I Q NHZ q in which B and Bindependently of one another represent a C C,,-alkyl, cycloalkyl oraralkyl radical, Hal and Haldenote a halogen atom, each of m and n is anumber from 0-3, with the proviso that the sum of m+n is at least I, andeach ofp and q is a number from 0-2; and the dyed materials aresubsequently subjected to a heat treatment.

The dyeings obtained are distinguished by high dyestuff yield, very goodbuild-up and excellent fastness properties, especially very goodfastness to thermofixing, washing, rubbing and light.

7 Claims, No Drawings PROCESS FOR THE CONTINUOUS DYEING OF SYNTHETICFIBER MATERIALS WITI-I DIPI-IENOXY ANTHRAQUINONE DYESTUFF S Theinvention relates to a process for the continuous dyeing of syntheticfiber materials from organic solvents; the process is characterized inthat the fiber materials are impregnated with dyeing liquors whichcontain anthraquinone dyestuffs of formula O NHz Hal) in which B and Bindependently of one another represent a C -C alkyl, cycloalkyl oraralkyl radical, preferably a C,C alkyl radical, Hal and Hal denote ahalogen atom, m and n are a number from 0-3, preferably a number froml2, with the proviso that the sum of n+m is at least 1, and p and qdenote a number from 0-2, preferably 0-1, and that the materials aresubsequently subjected to a heat treatment.

Possible halogen substituents Hal and Hal of the phenoxy radicals areespecially chlorine and bromine atoms.

As examples ofB and B there may be mentioned: as C,--C alkyl radicals,the methyl, ethyl, propyl, iso-propyl, iso-butyl, sec.-butyl,tert.-butyl, iso-amyl, sec.-pentyl, neopentyl, methyl-pentyl,dimethyl-butyl, methyl-hexyl, dimethyl-pentyl, trimethyl-butyl,iso-octyl, methyl-heptyl, dimethyl-hexyl, trimethyl-pentyl,tetramethyl-butyl, iso-nonyl, dimethyl-hepr tyl and trimethyl-hexylradical; as cycloalkyl radicals, the cyclohexyl and the methylcyclohexylradical and as aralkyl radicals, especially the benzyl and the a,a-dimethylbenzyl radical.

The dyestuffs used according to the invention for dyeing from organicsolvents are obtained according to processes which are in themselvesknown, for example by reaction ofl,4-diamino-2,B-dihalogen-anthraquinones with hydroxyaryl compoundswhich carry one or more alkyl or aralkyl or cycloalkyl radicalscontaining one to nine carbon atoms, in the presence of inorganic ororganic bases.

Possible organic water-immiscible solvents for the process according tothe invention are those of which the boiling points lie between 40 and170 C., for example aromatic hydrocarbons, such as toluene or xylene andhalogenated hydrocarbons, especially aliphatic chlorohydrocarbons, suchas methylene chloride, chloroform, carbon tetrachloride, 1,1-dichlorethane, 1,2-dichlorethane, 1,1 ,Z-trichlorethane, l,I,l,2-tetrachlorethane, 1, l ,2 ,2-tetrachlorethane, pentachlorethane,l-chloropropane 2-chlorpropane, 1,2- dichloropropane,1,1,l-trichloropropane, l-chlorbutane, 2- chlorobutane,1,4-dichlorobutane, l-chloro-2-methylpropane or 2-chloro-2-methylpropaneas well as aliphatic fluoroand fluorochloro-hydrocarbons, such asperfluoro-n-hexane, l,2,2-trifluorotrichlorethane and 1,1,l-trifluoropentachlorpropane, and aromatic chloroandfluoro-hydrocarbons such as chlorobenzene, fluorobenzene, chlorotolueneand benzotrifluoride.

Tetrachlorethylene, trichlorethylene and 1,1,1-

trichloroethane have proved particularly suitable. Mixtures of thesesolvents can also be used.

The synthetic fiber materials to be dyed according to the process of theinvention are especially fiber materials .of polyesters, for examplepolyethylene terephthalates or polyesters froml,4-bis-(hydroxymethyl)-cyclohexane and terephthalic acid, of, cellulosetriacetate, of synthetic polyamides such as poly-e-caprolactam,polyhexamethylenediamine adipate or poly-w-amino-undecane-acid, orpolyurethanes or of polyolefines. The fiber materials can be in the formof woven fabrics and knitted fabrics.

For dyeing, the dyestuffs to be used according to the invention aredissolved in organic solvents which are water-immiscible or added tothese in the form of solutions in solvents which are infinitely misciblewith these solvents, such as alcohols, dimethylformamide,dimethylacetamide, dimethylsulphoxide or sulpholane, and the syntheticfiber materials are impregnated with the resulting clear dyestuffsolutions which can optionally further contain soluble nonionicauxiliary agents, for example the known surface-active oxethylation andpropoxylation products of fatty alcohols, alkylphenols, fatty acidamides .and fatty acids, for improving the uniformity of the dyeings.Thereafter the dyestuffs are fixed on the fiber materials by a heattreatment. The heat treatment can consist of a brief dry heat treatmentat l20-230 C., with the dry heat treatment optionally being preceded byan intermediate drying, or can consist of a treatment of the fibermaterials in superheated solvent vapor at l00-l50 C. Small amounts ofnonfixed dyestuff can be eluted by brief treatment with the cold organicsolvent. It should be pointed out that mixtures of these dyestuff to beused according to the invention at times give better color yield thanthe individual dyestuffs and in certain cases show a better solubilityin the organic medium.

Using the process according to the invention it is possible, when dyeingfrom organic solvents, to achieve dyeings on synthetic fiber materialswhich are distinguished by high dyestuff yield, very good buildup andexcellent fastness properties, especially very good fastness tothermofixing, washing, rubbing and light. A further advantage of thedyestuffs to be used according to the invention is their high solubilityin organic solvents, especially in tetrachlorethylene, trichlorethylene,1,1,l-trichlorethane and 1,1,- trichloropropane, which makes it possibleto carry out the dyeing even without the use of solubilizing agents.

The parts indicated in the examples which follow are parts by weight.

EXAMPLE l A woven fabric of polyethylene terephthalate fibers isimpregnated at room temperature with a clear red-violet solution whichcontains 10 parts of l,4diamino-2,3-bis-(4-tert.-butylphenoxy)-anthraquinone in 990 parts oftetrachlorethylene. After squeezing out to a weight increase of 60percent, the woven fabric is dried for 1 minute at C. Thereafter thedyestuff is fixed by heating the woven fabric to l-220 C. for 45seconds. Thereafter the small amount of nonfixed dyestuff is eluted bybrief treatment in cold tetrachlorethylene for 20 seconds. After drying,a brilliant red-violet dyeing is obtained which is distinguished by itshigh dyestuff yield, very good build-up and excellent fastnessproperties, especially very good fastness to thermofixing, washing,rubbing and light.

Equivalent red-violet dyeings were also obtained analogously on wovenfabrics of (a) cellulose triacetate, (b) synthetic polyamides orpolyurethanes and (c) polypropylene fibers; the only difference was thatthe thermosol treatment was carried out at 200l4 220 C. for (a), atl70200 for (b) and at l20-150 C. for(c).

Equivalent dyeings were also obtained if the 990 parts oftetrachlorethylene were replaced by the same amount of one of thefollowing solvents: methylene chloride, chloroform, carbon tetrachloridedichlorethane, trichlorethane, trichlorethylene, tetrachlorethane,dichloropropane, 1,1,1- trichloropropane, chlorobutane, dichlorobutane,1,2,2- trifluorotrichlorethane and 1,1,ltrifluor-pentachloropropane,

The dyestuff used had been manufactured as follows:

Three hundred and fifty parts of 4-tert.-butylphenol and 38.4 parts ofpowdered potassium hydroxide were heated to C., with the water ofreaction being distilled off. 48.4 parts ofl,4-diamino-2,3-dichloro-anthraquinone were then introduced whilepassing in nitrogen. The reaction mixture was heated to l90-l95 C. untilno further starting material was chromatographically detectable. Afterdiluting the reaction mixture with methanol at 70 C., the dyestuff whichhad crystallized out in long needles was filtered off and washed withhot water until neutral. Yield: 81.4 parts.

The dyestuffs used in the Examples 2-which follow were manufacturedanalogously, except that instead of the 350 parts of 4-tert.-butylphenolthe equivalent amount of the phenols on which the phenoxy substituentsare based was employed.

EXAMPLE 2 A knitted fabric of polyhexamethylenediamine adipate filamentsis impregnated at room temperature with a clear redviolet solution whichcontains 10 parts of l,4-diamino-2,3-bis-(4-methylphenoxy)-anthraquinone and 7 parts ofnonylphenol-heptaglycol-ether in 983 parts of tetrachlorethylene. Aftersqueezing out to a weight increase of 60 percent, the knitted fabric isdried for 1 minute at 80 C. Thereafter the dyestuff is fixed by heatingthe knitted fabric to .192 C. for 45 seconds. Small amounts of nonfixeddyestuff EXAMPLE 3 A woven fabric of polypropylene fibers is impregnatedat room temperature with a clear red-violet solution which contains 10parts of l,4-diamino-2,3-bis-(3,5-diisopropyl-phenoxy)-anthroquinone and7 parts of nonylphenol-heptaglycolether in 983 parts oftetrachlorethylene. After squeezing out to a weight increase of 60percent, the woven fabric is dried for 1 minute at 80 C. Thereafter thedyestuff is fixed by heating the woven fabric to 140 C. for 30 seconds.Nonfixed amounts of dyestuff can be eluted by brief treatment in coldsolvent. A red-violet dyeing is obtained which is distinguished by highdyestuff yield, very good buildup and excellent fastness properties,especially very good fastness to thermofixing, washing, rubbing andlight.

EXAMPLE 4 A woven fabric of poly-1,4-cyclohexanedimethyleneterephthalate is impregnated at room temperature with a clear red-violetsolution which contains 10 parts of 1,4-diamino-2,3-bis-(4-isooctyl-phenoxy)anthraquinone and 7 partsofnonylphenol-heptaglycol-ether in 983 parts of tetrachlorethylene.After squeezing out to a weight increase of 60 percent, the woven fabricis dried for 1 minute at 80 C. Thereafter the dyestuff is fixed byheating the woven fabric to 190-220 C. for 45 seconds. The small amountof nonfixed dyestuff is then eluted by brief treatment in coldtetrachlorethylene for 20 seconds. After drying, a clear redvioletdyeing is obtained which is distinguished by its high dyestuff yield,very good buildup and excellent fastness properties, especially verygood fastness to thermofixing, washing, rubbing and light.

EXAMPLE 5 A woven fabric of polyethylene terephthalate fibers isimpregnated at room temperature with clear red-violet solution whichcontains parts of l,4-diamino-2,3-bis-(Z-methylphenoxy)-anthraquinone in990 parts of 1,l,l-trichlorethane. After squeezing out to a weightincrease of 60 percent, the dyestuff is fixed by treating the wovenfabric with superheated 1,1,1-trichlorethane vapor .at 140 C. for 45seconds. Thereafter the small amount of nonfixed dyestuff is eluted bybrief rinsing in cold 1,1,1-trichlorethane. After drying, redvioletdyeing is obtained which is distinguished by its high dyestuff yield,very good build-up and excellent fastness properties.

EXAMPLE 6 A woven fabric of poly-l ,4-cyclohexanedimethyleneterephthalate is impregnated at room temperature with a clear red-violetsolution which contains 10 parts of 1,4-diamino-2,3-bis-(3,4-dimethyl-phenoxy)-anthraquinone in 990 parts oftetrachlorethylene. After squeezing out to a weight increase of 60percent, the dyestuff is fixed by treating the woven fabric withsuperheated tetrachlorethylene vapor at 150 C. for 35 seconds. The smallamount of nonfixed dyestuff is then eluted by brief rinsing in coldtetrachlorethylene. After drying, a redviolet dyeing is obtained whichis distinguished by its high dyestuff yield, very good build-up andexcellent fastness properties.

Clear red-violet dyeings of excellent fastness properties on wovenfabrics of polyester, triacetate, polyamide, polyurethane andpolyolefine fibers were also obtained if instead of the dyestuffindicated, the same amount of a dyestuff indicated in the table whichfollows was used:

Example Dyestuff 7 l,4-diarnino-2,3-bis-(3-rnethyl-phenoxy)-anthraquinonc 8 l,4-diamino-2,3-bis-(2-ethyl-phenoxy)- anthraquinone 91,4-dlamino-2,3-bis(2,4-dimethylphenoxy)-anlhraquinonel,4-diamino-2,3-bis-( 2,6 dimethylphenoxy)-anlhraquinone lll,4-diamino-2,3-bis-(3,5-dimethylphcnoxy)-unthraquinoncI,4-diamino-2,3-bis-(4-chloro-3,S-dimethyl-phcnoxy)-anthraquinonel,4-diamino-2,3-bis-(2,5-dimethylphenoxy)-anthraquinone l,4-diamino2,3-bis-(2-isopropylphenoxyJ-anthruquinone1,4-diamino2,3-bis-(3-elhyl-5-methylphenoxyJ-nnlhraquinonc1,4-diamino-2,3-bis-(2-isobutylphenoxy)-anthraquinoncl,4-diamino-2,3-bis-( 4-isopropylphcnoxyyanthraquinone l,4-diamino-2,3-bis-( 2'isopropyl-3- methyhphenoxy)-anthraquinonel,4-diamino-2,3-bis-( 2-isopropyl-4- methyl-phenoxy)-unthraquinonel,4-diamino 2,3-bis-(4-isoamylphenuxy)- anthraquinonel,4-diaminc-2,3-bis-(4-isohexylphenoxyJ-anthraquinonel,4-diamino-2,3-bis-( 4-cyclohexylphenoxy)-anthraquinone 1,4-diamino-2,3-bis[4-( Z-phenyl-propyl- (2))-phenoxy]-anthraquinonel,4-diamino-2,3-bis( 4-benzyl-phenoxy)- anthraquinone l,4diamino-2,3-bis-(4-isononylphenoxyJ-anthraquinone Example 26 wovenfabric of cellulose triacetate fibers is impregnated at room temperaturewith a clear red-violet solution which contains 5 parts of the dyestuffdescribed in Example 1, 5 parts of the dyestuff described in Example 2and 7 parts of nonylphenol-heptaglycol-ether in 983 parts oftetrachlorethylene. After squeezing out to a weight increase of 60percent, the woven fabric is dried for 1 minute at C. Thereafterthedyestuff is fixed by heating the woven fabric to 215 C. for 1 minute. Abrilliant red-violet dyeing is obtained, which is distinguished by highdyestuff yield, very good buildup and excellent fastness properties,especially very good fast ness to thermofixing,washing, rubbing andlight.

Example 27 A woven fabric of anionically modified polyethyleneterephthalate fibers (Dacron 64) is impregnated at room temperature witha clear red-violet solution which contains parts of a mixture of theisomeric l,4-diamino-2,3-bis-cresoxy-anthraquinones and 7 parts ofnonylphenol-heptaglycolether in 983 parts of tetrachlorethylene. Aftersqueezing out to a weight increase of 60 percent, the woven fabric isdried for 1 minute at 80 C. and the dyestuff is fixed by heating thewoven fabric to l90-220 C. for 1 minute. A brilliant redviolet dyeing isobtained, which is distinguished by very good dyestuff yield, very goodbuildup and excellent fastness pro perties, especially very goodfastness to thermofixing, washing, rubbing and light.

Equivalent red-violet dyeings were also obtained on woven fabrics ofanionically modified polyhexamethylenediamine adipate fibers (Nylon T844).

The dyestuff mixture used had been manufactured as follows:

One hundred and sixty parts of a mixture of equal parts of the isomericcresols were heated to 150 C. with 19 parts of potassium hydroxide, withthe water of reaction being distilled off. 24.2 parts ofl,4-diamino-2,SdichIor-anthraquinone were then introduced undernitrogen. The reaction mixture was heated to 190195 C. for 20 hours andsubsequently stirred into dilute sodium hydroxide solution. The dyestuffmixture which precipitated as an oil was separated off in a separatingfunnel and twice extracted by shaking with methanol. After drying invacuo, 18 parts of dyestuff mixture were obtained.

We claim:

1. Process for the continuous dyeing of synthetic fiber materials fromorganic solvents, which comprises impregnating said fiber materials withorganic solvent dyeing liquors which contain anthraquinone dyestuffs offormula 1 um'iq in which B and B independently of one another representa C C,,

alkyl, cycloalkyl or aralkyl radical, Hal and Hal denote a halogen atom,m and n are a number from 0-3, with the proviso that the sum of n+m isat least 1, and p and q denote a number from 0-2, and that the materialsare subsequently subjected to a heat treatment.

2. Process according to claim 1 wherein m and n have the significanceindicated in claim 1 and B and B independently of one another denote a CC alkyl group, and p and q is a number from 0-1 3. Process according toclaim 1 wherein said anthraquione dyestuff is1,4-diamino-2,3-bis-cresoxy-anthraquinone.

4. Process according to claim 1 wherein said anthraquione dyestuff isl,4-diamino-2,3-bis-(ethy1-phenoxy)-anthraquinone.

5. Process according to claim 1 wherein said anthraquione dyestuff isl,4-diamino-2,3-bis-(dimethyl-phenoxy)- anthraquinone.

6. Process according to claim 1 wherein said anthraquione dyestuff isl,4-diamino-2,3bis-( isopropyl-phenoxy anthraquinone.

7. Synthetic fiber materials dyed according to claim 1.

2. Process according to claim 1 wherein m and n have the significanceindicated in claim 1 and B and B'' independently of one another denote aC1-C5-alkyl group, and p and q is a number from 0-1.
 3. Processaccording to claim 1 wherein said anthraquione dyestuff is1,4-diamino-2,3-bis-cresoxy-anthraquinone.
 4. Process according to claim1 wherein said anthraquione dyestuff is1,4-diamino-2,3-bis-(ethyl-phenoxy)-anthraquinone.
 5. Process accordingto claim 1 wherein said anthraquione dyestuff is1,4-diamino-2,3-bis-(dimethyl-phenoxy)-anthraquinone.
 6. Processaccording to claim 1 wherein said anthraquione dyestuff is1,4-diamino-2,3bis-(isopropyl-phenoxy)-anthraquinone.
 7. Synthetic fibermaterials dyed according to claim 1.